Halogenation of Carbonyl Compounds
361
General Experimental Procedure for α-Halogenation of
Carbonyl Compounds by [AcMIm]X and CAN
(f) H. M. Meshram, P. N. Reddy, P. Vishnu, K. Sadashiv,
J. S. Yadav, Tetrahedron Lett. 2006, 47, 991, and references therein.
doi:10.1016/J.TETLET.2005.11.141
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S-1981-29432
Representative Procedure for 2-Chlorocyclohexanone
(Entry 2a, Table 1)
Ceric ammonium nitrate (1.09 g, 2 mmol) was added to a
mixture of cyclohexanone (98 mg, 1 mmol) and [AcMIm]X[5k]
(168 mg, 1.2 mmol), and the whole mixture was then stirred
at room temperature (25–28◦C) under nitrogen for 4 h (TLC).
The reaction mixture was quenched with water and extracted
with ethyl acetate (2 × 10 mL). The extract was successively
washed with saturated NaHCO3 solution, water, brine, and dried
(Na2SO4). Evaporation of solvent left the crude product, which
was purified by column chromatography over silica gel to pro-
vide pure 2-chlorocyclohexanone (119 mg, 90%) as a colourless
liquid.The product was easily identified by its spectroscopic data
(IR, 1H NMR, and 13C NMR), which are in complete agreement
with those reported for an authentic sample.[2f] All of the prod-
ucts except two are known compounds[2,6,7–12] and are easily
identified by comparison of their NMR spectra with those of
authentic samples (see references in Table 1). The purity of all
compounds was checked by 1H and 13C NMR spectra and ele-
mental analysis.The new compounds were characterized by their
spectroscopic data (IR, 1H NMR, and 13C NMR) and elemental
analysis. These values are reported below:
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2664.
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1-Chloro-3-methyl-2-oxocyclohexanecarboxylic Acid
Methyl Ester (Entry 20a, Table 1)
[3] R. P. Swatloski, J. D. Holbrey, R. D. Rogers, Green Chem. 2003, 5,
361. doi:10.1039/B304400A
[4] (a) T. Welton Chem. Rev. 1999, 99, 2071. doi:10.1021/CR980032T
(b) P. Wasserscheid, W. Keim, Angew. Chem. Int. Ed. 2000,
39, 3773. doi:10.1002/1521-3773(20001103)39:21<3772::AID-
ANIE3772>3.0.CO;2-5
Colourless liquid (one stereoisomer). νmax/cm−1 1741, 1720,
1437, 1269, 1252, 1097. δH 3.85 (s, 3H), 2.57–2.64 (m, 2H),
2.31–2.37 (m, 1H), 2.06–2.16 (m, 2H), 1.77–1.85 (m, 2H), 1.05
(d, J 6.5, 3H). δC 204.0, 168.5, 73.3, 53.8, 40.1, 39.1, 36.1,
20.8, 14.8. Found: C 52.8, H 6.6. Calc. for C9H13ClO3: C 52.8,
H 6.4%.
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doi:10.1021/JO035038J
(f) D.-G. Gu, S.-J. Ji, Z.-Q. Jiang, M.-F. Zhou, T.-P. Loh, Synlett
2005, 959.
1-Bromo-3-methyl-2-oxocyclohexanecarboxylic Acid
Methyl Ester (Entry 20b, Table 1)
Colourless liquid (one stereoisomer). νmax/cm−1 1741, 1733,
1452, 1356, 1215, 1084. δH 3.72 (s, 3H), 2.30–2.35 (m, 1H),
1.98–2.13 (m, 2H), 1.67–1.77 (m, 2H), 1.31–1.38 (m, 2H), 1.07
(d, J 6.3, 3H). δC 199.3, 168.3, 68.3, 53.6, 44.3, 42.1, 35.7,
24.3, 15.2. Found: C 43.3, H 5.3. Calc. for C9H13BrO3: C 43.4,
H 5.3%.
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Acknowledgments
This investigation has enjoyed financial support from CSIR, New Delhi
[grant no. 01(1936)/04]. L.A. and S.B. also thank CSIR for their fellowships.
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